CN112313285B - Urethane resin composition, surface treatment agent and article - Google Patents
Urethane resin composition, surface treatment agent and article Download PDFInfo
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- CN112313285B CN112313285B CN201980041730.7A CN201980041730A CN112313285B CN 112313285 B CN112313285 B CN 112313285B CN 201980041730 A CN201980041730 A CN 201980041730A CN 112313285 B CN112313285 B CN 112313285B
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- urethane resin
- parts
- resin composition
- surface treatment
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 90
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 24
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 28
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims description 8
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims 4
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 45
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 39
- 150000003077 polyols Chemical class 0.000 description 29
- 238000000034 method Methods 0.000 description 26
- 239000005056 polyisocyanate Substances 0.000 description 26
- 229920001228 polyisocyanate Polymers 0.000 description 26
- 229920005862 polyol Polymers 0.000 description 25
- 239000006185 dispersion Substances 0.000 description 22
- 239000003431 cross linking reagent Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000004970 Chain extender Substances 0.000 description 17
- 238000005299 abrasion Methods 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 12
- 229920000515 polycarbonate Polymers 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 125000002723 alicyclic group Chemical group 0.000 description 10
- 150000001718 carbodiimides Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
- 239000011325 microbead Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920002397 thermoplastic olefin Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- HSZGXYFZPBCFSP-UHFFFAOYSA-N 2,6-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(N)=C1S(O)(=O)=O HSZGXYFZPBCFSP-UHFFFAOYSA-N 0.000 description 1
- IVGRSQBDVIJNDA-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanesulfonic acid Chemical compound NCCNCCS(O)(=O)=O IVGRSQBDVIJNDA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- SPGHPHFQNQIZME-UHFFFAOYSA-N 2-n-ethylethane-1,1,2-triamine Chemical class CCNCC(N)N SPGHPHFQNQIZME-UHFFFAOYSA-N 0.000 description 1
- YUZJZPMLAIYVGM-UHFFFAOYSA-N 2-n-methylethane-1,1,2-triamine Chemical class CNCC(N)N YUZJZPMLAIYVGM-UHFFFAOYSA-N 0.000 description 1
- JIRLWRUWVNHTQG-UHFFFAOYSA-N 3,4-diaminobutane-1-sulfonic acid Chemical compound NCC(N)CCS(O)(=O)=O JIRLWRUWVNHTQG-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- XJIIBKORMYCKON-UHFFFAOYSA-N 3,6-diamino-2-methylbenzenesulfonic acid Chemical compound CC1=C(N)C=CC(N)=C1S(O)(=O)=O XJIIBKORMYCKON-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
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- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
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- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
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- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/42—Gloss-reducing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明提供一种氨基甲酸酯树脂组合物，其特征在于，含有氨基甲酸酯树脂(A)、水(B)和数均分子量为15万以上且小于33万的硅酮化合物(C)。另外，本发明提供表面处理剂和物品，所述表面处理剂的特征在于含有上述氨基甲酸酯树脂组合物，所述物品的特征在于具有通过该表面处理剂而形成的层。上述硅酮化合物(C)的含量优选为0.01～10质量％的范围。上述硅酮化合物(C)优选为聚二甲基硅氧烷。上述硅酮化合物(C)优选为聚二甲基硅氧烷。优选在上述表面处理剂中进一步含有填料(D)。The present invention provides a urethane resin composition, which is characterized in that it contains a urethane resin (A), water (B) and a silicone compound (C) with a number average molecular weight of not less than 150,000 and less than 330,000 . In addition, the present invention provides a surface treatment agent characterized by containing the above-mentioned urethane resin composition, and an article characterized by having a layer formed by the surface treatment agent. The content of the silicone compound (C) is preferably in the range of 0.01 to 10% by mass. The aforementioned silicone compound (C) is preferably polydimethylsiloxane. The aforementioned silicone compound (C) is preferably polydimethylsiloxane. It is preferable to further contain a filler (D) in the above-mentioned surface treatment agent.
Description
技术领域technical field
本发明涉及氨基甲酸酯树脂组合物、表面处理剂及具有利用表面处理剂形成的层的物品。The present invention relates to a urethane resin composition, a surface treatment agent, and an article having a layer formed using the surface treatment agent.
背景技术Background technique
在汽车内部装饰皮革用片材的制造工序中，从赋予耐化学试剂性和外观设计性的观点出发，利用表面处理剂对其表面进行精加工。现有的表面处理剂中使用的材料以包含有机溶剂的溶剂系树脂组合物为主流，但受到近年来环境限制的提高，正在推进实质上不含有有机溶剂的水性表面处理剂的开发。In the production process of the automotive interior leather sheet, the surface is finished with a surface treatment agent from the viewpoint of imparting chemical resistance and designability. The materials used in conventional surface treatment agents are mainly solvent-based resin compositions containing organic solvents, but due to the increase in environmental restrictions in recent years, the development of water-based surface treatment agents that do not substantially contain organic solvents is being promoted.
作为上述水性表面处理剂，例如公开了含有具有特定的机械物理性质的氨基甲酸酯、碳二亚胺交联剂和填料的水性表面处理剂(例如，参照专利文献1)。然而，如果将现有的溶剂系树脂组合物水系化，则存在耐磨损性降低的问题，上述水性表面处理剂的表面的摩擦系数也高，要求进一步改善耐磨损性。As said aqueous surface treatment agent, the aqueous surface treatment agent containing the carbamate which has specific mechanical physical property, a carbodiimide crosslinking agent, and a filler is disclosed, for example (for example, refer patent document 1). However, if the conventional solvent-based resin composition is water-based, there is a problem that the wear resistance is lowered, and the friction coefficient of the surface of the above-mentioned water-based surface treatment agent is also high, and further improvement of the wear resistance is required.
现有技术文献prior art literature
专利文献patent documents
专利文献1：国际公开第2015/107933号公报Patent Document 1: International Publication No. 2015/107933
发明内容Contents of the invention
发明要解决的课题The problem to be solved by the invention
本发明要解决的课题在于提供一种含有水、且能够得到耐磨损性优异的覆膜的氨基甲酸酯树脂组合物。The problem to be solved by the present invention is to provide a urethane resin composition containing water and capable of obtaining a coating film excellent in abrasion resistance.
用于解决课题的手段means to solve the problem
本发明提供一种氨基甲酸酯树脂组合物，其特征在于，含有氨基甲酸酯树脂(A)、水(B)和数均分子量为15万以上且小于33万的硅酮化合物(C)。The present invention provides a urethane resin composition, which is characterized in that it contains a urethane resin (A), water (B) and a silicone compound (C) with a number average molecular weight of not less than 150,000 and less than 330,000 .
另外，本发明提供表面处理剂和物品，所述表面处理剂的特征在于含有上述氨基甲酸酯树脂组合物，所述物品的特征在于具有利用该表面处理剂而形成的层。In addition, the present invention provides a surface treatment agent characterized by containing the above-mentioned urethane resin composition, and an article characterized by having a layer formed using the surface treatment agent.
发明的效果The effect of the invention
本发明的氨基甲酸酯树脂组合物能够得到耐化学试剂性优异的覆膜。因此，本发明的氨基甲酸酯树脂组合物能够适合用作各种物品的表面处理剂。The urethane resin composition of the present invention can obtain a coating film excellent in chemical resistance. Therefore, the urethane resin composition of the present invention can be suitably used as a surface treatment agent for various articles.
具体实施方式Detailed ways
本发明的氨基甲酸酯树脂组合物含有氨基甲酸酯树脂(A)、水(B)和具有特定的数均分子量的硅酮化合物(C)。The urethane resin composition of the present invention contains a urethane resin (A), water (B), and a silicone compound (C) having a specific number average molecular weight.
上述氨基甲酸酯树脂(A)能够分散于水(B)中，例如可以使用：具有阴离子性基团、阳离子性基团、非离子性基团等亲水性基团的氨基甲酸酯树脂；用乳化剂强制分散于水(B)中的氨基甲酸酯树脂等。这些氨基甲酸酯树脂(A)可以单独使用，也可以并用2种以上。The above-mentioned urethane resin (A) can be dispersed in water (B), and for example, a urethane resin having hydrophilic groups such as anionic groups, cationic groups, and nonionic groups can be used ; A urethane resin or the like that is forcibly dispersed in water (B) with an emulsifier. These urethane resins (A) may be used alone or in combination of two or more.
作为得到上述具有阴离子性基团的氨基甲酸酯树脂的方法，例如可举出使用选自具有羧基的化合物和具有磺酰基的化合物中的1种以上的化合物作为原料的方法。As a method of obtaining the urethane resin which has the said anionic group, the method of using one or more types of compounds selected from the compound which has a carboxyl group and the compound which has a sulfonyl group as a raw material is mentioned, for example.
作为上述具有羧基的化合物，例如可以使用2，2-二羟甲基丙酸、2，2-二羟甲基丁酸、2，2-二羟甲基酪酸、2，2-二羟甲基丙酸、2，2-戊酸等。这些化合物可以单独使用，也可以并用2种以上。As the above-mentioned compound having a carboxyl group, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylol Propionic acid, 2,2-pentanoic acid, etc. These compounds may be used alone or in combination of two or more.
作为上述具有磺酰基的化合物，例如可以使用：3，4-二氨基丁烷磺酸、3，6-二氨基-2-甲苯磺酸、2，6-二氨基苯磺酸、N-(2-氨基乙基)-2-氨基乙基磺酸等。这些化合物可以单独使用，也可以并用2种以上。As the above-mentioned compound having a sulfonyl group, for example, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2 -aminoethyl)-2-aminoethylsulfonic acid and the like. These compounds may be used alone or in combination of two or more.
在树脂组合物中，上述羧基和磺酰基的一部分或全部可以被碱性化合物中和。作为上述碱性化合物，例如可以使用氨、三乙胺、吡啶、吗啉等有机胺；单乙醇胺、二甲基乙醇胺等烷醇胺；包含钠、钾、锂、钙等的金属碱化合物等。In the resin composition, some or all of the aforementioned carboxyl groups and sulfonyl groups may be neutralized with a basic compound. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; metal alkali compounds containing sodium, potassium, lithium, calcium, and the like.
作为得到上述具有阳离子性基团的氨基甲酸酯树脂的方法，例如可举出使用1种或2种以上的具有氨基的化合物作为原料的方法。As a method of obtaining the urethane resin which has the said cationic group, the method of using 1 type, or 2 or more types of compounds which have an amino group as a raw material is mentioned, for example.
作为上述具有氨基的化合物，例如可以使用：三亚乙基四胺、二亚乙基三胺等具有伯氨基和仲氨基的化合物；N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二氨基乙基胺、N-乙基二氨基乙基胺等N-烷基二氨基烷基胺等具有叔氨基的化合物等。这些化合物可以单独使用，也可以并用2种以上。As the above-mentioned compounds having amino groups, for example: compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkanes such as N-methyldiethanolamine and N-ethyldiethanolamine; Compounds having a tertiary amino group such as N-alkyldiaminoalkylamines such as alkyl dialkanolamines, N-methyldiaminoethylamines, and N-ethyldiaminoethylamines. These compounds may be used alone or in combination of two or more.
作为得到上述具有非离子性基团的氨基甲酸酯树脂的方法，例如可举出使用1种或2种以上的具有氧乙烯结构(日文：オキシエ于レン構造)的化合物作为原料的方法。As a method of obtaining the above-mentioned urethane resin having a nonionic group, for example, a method of using one or more compounds having an oxyethylene structure (Japanese: Okishie Uren structure) as a raw material is mentioned.
作为上述具有氧乙烯结构的化合物，例如可以使用：聚氧乙烯二醇、聚氧乙烯聚氧丙烯二醇、聚氧乙烯聚氧四亚甲基二醇等具有氧乙烯结构的聚醚多元醇。这些化合物可以单独使用，也可以并用2种以上。As the compound having an oxyethylene structure, for example, polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.
作为用于制造以上的具有亲水性基团的氨基甲酸酯树脂的原料的使用量，从得到更优异的耐化学试剂性、耐磨损性、耐候性和耐水解性的观点出发，优选为氨基甲酸酯树脂(A)的原料中0.1～15质量％的范围，更优选为1～10质量％的范围，进一步优选为1.5～7质量％的范围。As the usage amount of the raw material for producing the above urethane resin having a hydrophilic group, from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, weather resistance and hydrolysis resistance, preferably It is the range of 0.1-15 mass % in the raw material of a urethane resin (A), More preferably, it is the range of 1-10 mass %, More preferably, it is the range of 1.5-7 mass %.
作为在得到上述强制地分散于水(B)中的氨基甲酸酯树脂时可以使用的乳化剂，例如可以使用：聚氧乙烯壬基苯基醚、聚氧乙烯月桂基醚、聚氧乙烯苯乙烯基苯基醚、聚氧乙烯山梨糖醇四油酸酯、聚氧乙烯-聚氧丙烯共聚物等非离子性乳化剂；油酸钠等脂肪酸盐、烷基硫酸酯盐、烷基苯磺酸盐、烷基磺基琥珀酸盐、萘磺酸盐、聚氧乙烯烷基硫酸盐、烷烃磺酸钠盐、烷基二苯基醚磺酸钠盐等阴离子性乳化剂；烷基胺盐、烷基三甲基铵盐、烷基二甲基苄基铵盐等阳离子性乳化剂等。这些乳化剂可以单独使用，也可以并用2种以上。As an emulsifier that can be used to obtain the above-mentioned urethane resin forcibly dispersed in water (B), for example, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene benzene Non-ionic emulsifiers such as vinyl phenyl ether, polyoxyethylene sorbitan tetraoleate, polyoxyethylene-polyoxypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene Sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, polyoxyethylene alkyl sulfate, alkane sulfonate sodium salt, alkyl diphenyl ether sulfonate sodium salt and other anionic emulsifiers; alkylamine cationic emulsifiers such as salts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, etc. These emulsifiers may be used alone or in combination of two or more.
作为上述氨基甲酸酯树脂(A)，具体而言，例如可以使用：用于制造上述具有亲水性基团的氨基甲酸酯树脂的原料、多异氰酸酯(a1)、多元醇(a2)和扩链剂(a3)的反应物。它们的反应可以使用公知的氨基甲酸酯化反应。As the above-mentioned urethane resin (A), specifically, for example, raw materials for producing the above-mentioned urethane resin having a hydrophilic group, polyisocyanate (a1), polyol (a2) and Reactant for chain extender (a3). These reactions can use well-known urethanization reaction.
作为上述多异氰酸酯(a1)，例如可以使用：亚苯基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、萘二异氰酸酯、多亚甲基多苯基多异氰酸酯、碳二亚胺化二苯基甲烷多异氰酸酯等芳香族多异氰酸酯；六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、二聚酸二异氰酸酯、降冰片烯二异氰酸酯等脂肪族或脂环式多异氰酸酯等。这些多异氰酸酯可以单独使用，也可以并用2种以上。As the polyisocyanate (a1), for example, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, etc. , Carbodiimidized diphenylmethane polyisocyanate and other aromatic polyisocyanates; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate , xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate and other aliphatic or alicyclic polyisocyanates, etc. These polyisocyanates may be used alone or in combination of two or more.
作为上述多异氰酸酯(a1)，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选使用脂环式多异氰酸酯，更优选使用至少具有1个以上的异氰酸酯基的氮原子与环己烷环直接连结的结构的多异氰酸酯，进一步优选使用异佛尔酮二异氰酸酯和/或二环己基甲烷二异氰酸酯。另外，作为脂环式多异氰酸酯的使用量，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选为多异氰酸酯(a1)中30质量％以上，更优选为40质量％以上，进一步优选为50质量％以上。As the above-mentioned polyisocyanate (a1), it is preferable to use an alicyclic polyisocyanate from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, and it is more preferable to use a nitrogen compound having at least one isocyanate group. As a polyisocyanate having a structure in which atoms are directly linked to a cyclohexane ring, it is more preferable to use isophorone diisocyanate and/or dicyclohexylmethane diisocyanate. In addition, the amount of alicyclic polyisocyanate used is preferably 30% by mass or more in the polyisocyanate (a1), more preferably 40% by mass, from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. % by mass or more, more preferably 50% by mass or more.
另外，在将本发明的氨基甲酸酯树脂组合物用作表面处理剂时，在要求更进一步的耐光性的情况下，作为上述多异氰酸酯(a1)，优选并用上述脂环式多异氰酸酯和脂肪族多异氰酸酯，作为上述脂肪族多异氰酸酯，优选使用六亚甲基二异氰酸酯。作为此时的多异氰酸酯(a1)中的上述脂环式多异氰酸酯的含量，优选为30质量％以上，更优选为40质量％以上，进一步优选为50质量％以上。In addition, when the urethane resin composition of the present invention is used as a surface treatment agent, when further light resistance is required, as the polyisocyanate (a1), it is preferable to use the above-mentioned alicyclic polyisocyanate and an aliphatic polyisocyanate in combination. As the aliphatic polyisocyanate, hexamethylene diisocyanate is preferably used as the above-mentioned aliphatic polyisocyanate. The content of the alicyclic polyisocyanate in the polyisocyanate (a1) at this time is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more.
作为上述多异氰酸酯(a1)的使用量，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选为氨基甲酸酯树脂(A)的原料中5～50质量％的范围，更优选为15～40质量％的范围，进一步优选为20～37质量％的范围。The amount of the polyisocyanate (a1) used is preferably 5 to 50% by mass in the raw material of the urethane resin (A) from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. The range of 15-40 mass % is more preferable, and the range of 20-37 mass % is still more preferable.
作为上述多元醇(a2)，例如可以使用：聚醚多元醇、聚酯多元醇、聚丙烯酸系多元醇、聚碳酸酯多元醇、聚丁二烯多元醇等。这些多元醇可以单独使用，也可以并用2种以上。其中，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选使用聚碳酸酯多元醇。As said polyol (a2), for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, etc. can be used. These polyols may be used alone or in combination of two or more. Among them, polycarbonate polyol is preferably used from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance.
作为上述聚碳酸酯多元醇，例如可以使用碳酸酯和/或光气与具有2个以上羟基的化合物的反应物。As said polycarbonate polyol, the reactant of carbonate and/or phosgene, and the compound which has 2 or more hydroxyl groups can be used, for example.
作为上述碳酸酯，例如可以使用碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、碳酸亚乙酯、碳酸亚丙酯等。这些化合物可以单独使用，也可以并用2种以上。As said carbonate, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. can be used. These compounds may be used alone or in combination of two or more.
作为上述具有2个以上羟基的化合物，例如可以使用：乙二醇、丙二醇、1，3-丙二醇、1，4-丁二醇、1，3-丁二醇、1，2-丁二醇、2-甲基-1，3-丙二醇、1，5-戊二醇、新戊二醇、1，6-己二醇、1，5-己二醇、3-甲基-1，5-戊二醇、1，7-庚二醇、1，8-辛二醇、1，9-壬二醇、1，8-壬二醇、2-乙基-2-丁基-1，3-丙二醇、1，10-癸二醇、1，12-十二烷二醇、1，4-环己烷二甲醇、1，3-环己烷二甲醇、三羟甲基丙烷、3-甲基戊二醇、新戊二醇、三羟甲基乙烷、甘油等。这些化合物可以单独使用，也可以并用2种以上。其中，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选使用选自1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、1，4-环己烷二甲醇、3-甲基戊二醇和1，10-癸二醇中的1种以上的化合物，更优选1，6-己二醇。As the compound having two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol Diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol , 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, 3-methylpentane Glycol, neopentyl glycol, trimethylolethane, glycerin, etc. These compounds may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, it is preferable to use 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 1 or more compounds selected from 6-hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol and 1,10-decanediol, more preferably 1,6-hexanediol.
作为上述聚碳酸酯多元醇的使用量，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选为多元醇(a2)中85质量％以上，更优选为90质量％以上，进一步优选为95质量％以上。The amount of the polycarbonate polyol used is preferably 85% by mass or more in the polyol (a2), more preferably 90% by mass, from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. % or more, more preferably 95% by mass or more.
作为上述聚碳酸酯多元醇的数均分子量，从得到更优异的耐化学试剂性、机械强度、耐磨损性和耐候性的观点出发，优选为100～100000的范围，更优选为150～10000的范围，进一步优选为200～2500的范围。应予说明，上述聚碳酸酯多元醇的数均分子量表示通过凝胶渗透色谱(GPC)法所测得的值。The number average molecular weight of the polycarbonate polyol is preferably in the range of 100 to 100,000, more preferably 150 to 10,000, from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance. The range of 200-2500 is more preferable. In addition, the number average molecular weight of the said polycarbonate polyol shows the value measured by the gel permeation chromatography (GPC) method.
作为上述聚碳酸酯多元醇以外的上述多元醇(a2)的数均分子量，从得到更优异的耐候性的观点出发，优选为500～100000的范围，更优选为700～50000的范围，进一步优选为800～10000的范围。应予说明，上述多元醇(a2)的数均分子量表示通过凝胶渗透色谱(GPC)法所测得的值。The number average molecular weight of the polyol (a2) other than the polycarbonate polyol is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 50,000, and still more preferably It is in the range of 800 to 10000. In addition, the number average molecular weight of the said polyol (a2) shows the value measured by the gel permeation chromatography (GPC) method.
作为上述多元醇(a2)的使用量，优选为氨基甲酸酯树脂(A)的原料中30～80质量％的范围，更优选为40～75质量％的范围，进一步优选为50～70质量％的范围。The amount of the polyol (a2) used is preferably in the range of 30 to 80% by mass, more preferably in the range of 40 to 75% by mass, and still more preferably in the range of 50 to 70% by mass in the raw material of the urethane resin (A). % range.
作为上述扩链剂(a3)，例如为数均分子量为50～450的范围的扩链剂(不包括上述聚碳酸酯多元醇)，具体而言，可以使用：乙二胺、1，2-丙二胺、1，6-六亚甲基二胺、哌嗪、2，5-二甲基哌嗪、异佛尔酮二胺、1，2-环己烷二胺、1，3-环己烷二胺、1，4-环己烷二胺、4，4’-二环己基甲烷二胺、3，3’-二甲基-4，4’-二环己基甲烷二胺、1，4-环己烷二胺、肼等具有氨基的扩链剂；乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、1，3-丙二醇、1，3-丁二醇、1，4-丁二醇、六亚甲基二醇、蔗糖、甲二醇、甘油、山梨糖醇、双酚A、4，4’-二羟基联苯、4，4’-二羟基二苯基醚、三羟甲基丙烷等具有羟基的扩链剂等。这些扩链剂可以单独使用，也可以并用2种以上。As the above-mentioned chain extender (a3), for example, a chain extender (excluding the above-mentioned polycarbonate polyol) having a number average molecular weight of 50 to 450, specifically, ethylenediamine, 1,2-propane Diamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexane Alkanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4 -Chain extenders with amino groups such as cyclohexanediamine and hydrazine; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1 , 4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl A chain extender having a hydroxyl group such as ether and trimethylolpropane, etc. These chain extenders may be used alone or in combination of two or more.
作为上述扩链剂(a3)，其中，从得到更优异的耐化学试剂性、机械强度、耐磨损性和耐候性的观点出发，优选使用具有氨基的扩链剂，更优选为哌嗪和/或肼，作为哌嗪和肼的总量，优选为上述扩链剂(a3)中30质量％以上，更优选为50质量％以上，进一步优选为60质量％以上，特别优选为80质量％以上。另外，作为上述扩链剂(a3)，优选平均官能团数小于3，更优选小于2.5。另外，As the above-mentioned chain extender (a3), among them, from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, abrasion resistance and weather resistance, it is preferable to use a chain extender having an amino group, more preferably piperazine and And/or hydrazine, the total amount of piperazine and hydrazine is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 80% by mass in the above-mentioned chain extender (a3) above. In addition, as the chain extender (a3), the average number of functional groups is preferably less than 3, more preferably less than 2.5. in addition,
作为上述扩链剂(a3)的使用量，从得到更优异的耐化学试剂性、机械强度、耐磨损性和耐候性的观点出发，优选为氨基甲酸酯树脂(A)的原料中0.5～10质量％的范围，更优选为0.7～5质量％的范围，进一步优选为0.9～2.3的范围。As the usage-amount of the above-mentioned chain extender (a3), from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, wear resistance, and weather resistance, it is preferably 0.5% of the raw material of the urethane resin (A). The range of ˜10% by mass, more preferably the range of 0.7-5% by mass, and still more preferably the range of 0.9-2.3% by mass.
作为上述氨基甲酸酯树脂(A)的制造方法，例如可举出如下方法：通过使上述多异氰酸酯(a1)、上述多元醇(a2)、和用于制造上述具有亲水性基团的氨基甲酸酯树脂的原料反应来制造具有异氰酸酯基的氨基甲酸酯预聚物，接下来，通过使上述氨基甲酸酯预聚物与上述扩链剂(a3)反应来进行制造的方法；一次性加入上述多异氰酸酯(a1)、上述多元醇(a2)、用于制造具有亲水性基团的氨基甲酸酯树脂的原料和上述扩链剂(a3)并使之反应的方法等。这些反应例如可举出在50～100℃进行3～10小时。As a method for producing the above-mentioned urethane resin (A), for example, the following method is mentioned: by making the above-mentioned polyisocyanate (a1), the above-mentioned polyol (a2), and the amino group used to produce the above-mentioned hydrophilic group A method of producing a urethane prepolymer having an isocyanate group by reacting raw materials of a formate resin, and then, reacting the above-mentioned urethane prepolymer with the above-mentioned chain extender (a3); once A method in which the polyisocyanate (a1), the polyol (a2), raw materials for producing a urethane resin having a hydrophilic group, and the chain extender (a3) are added and reacted. These reactions include, for example, performing at 50 to 100° C. for 3 to 10 hours.
就用于制造上述具有亲水性基团的氨基甲酸酯树脂的原料所具有的羟基、上述多元醇(a2)所具有的羟基及上述扩链剂(a3)所具有的羟基和氨基的合计与上述多异氰酸酯(a1)所具有的异氰酸酯基的摩尔比[(异氰酸酯基)/(羟基和氨基)]而言，优选为0.8～1.2的范围，更优选为0.9～1.1的范围。The total of the hydroxyl groups of the raw materials used to produce the above-mentioned urethane resin having a hydrophilic group, the hydroxyl groups of the above-mentioned polyol (a2), and the hydroxyl groups and amino groups of the above-mentioned chain extender (a3) The molar ratio [(isocyanate group)/(hydroxyl group and amino group)] to the isocyanate group contained in the polyisocyanate (a1) is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.
在制造上述氨基甲酸酯树脂(A)时，优选使残留于上述氨基甲酸酯树脂(A)中的异氰酸酯基失活。在使上述异氰酸酯基失活的情况下，优选使用甲醇等具有1个羟基的醇。作为上述醇的使用量，相对于氨基甲酸酯树脂(A)100质量份，优选为0.001～10质量份的范围。When producing the above-mentioned urethane resin (A), it is preferable to inactivate the isocyanate group remaining in the above-mentioned urethane resin (A). When deactivating the above-mentioned isocyanate group, it is preferable to use an alcohol having one hydroxyl group, such as methanol. As the usage-amount of the said alcohol, it is preferable that it is the range of 0.001-10 mass parts with respect to 100 mass parts of urethane resins (A).
另外，在制造上述氨基甲酸酯树脂(A)时，可以使用有机溶剂。作为上述有机溶剂，例如可以使用：丙酮、甲乙酮等酮化合物；四氢呋喃、二噁烷等醚化合物；乙酸乙酯、乙酸丁酯等乙酸酯化合物；乙腈等腈化合物；二甲基甲酰胺、N-甲基吡咯烷酮等酰胺化合物等。这些有机溶剂可以单独使用，也可以并用2种以上。应予说明，上述有机溶剂优选通过蒸馏法等最终被除去。Moreover, an organic solvent can be used at the time of manufacture of the said urethane resin (A). As the above-mentioned organic solvent, for example, ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; - Amide compounds such as methylpyrrolidone, etc. These organic solvents may be used alone or in combination of two or more. In addition, it is preferable to finally remove the above-mentioned organic solvent by distillation or the like.
作为上述氨基甲酸酯树脂(A)的氨基甲酸酯键的含量，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选为980～4000mmol/kg的范围，更优选为1000～3500mmol/kg的范围，进一步优选为1100～3000mmol/kg的范围，1150～2500mmol/kg的范围。应予说明，上述氨基甲酸酯树脂(A)的氨基甲酸酯键的含量表示根据上述多异氰酸酯(a1)、多元醇(a2)、用于制造具有亲水性基团的氨基甲酸酯树脂的原料和扩链剂(a3)的加入量而算出的值。The urethane bond content of the urethane resin (A) is preferably in the range of 980 to 4000 mmol/kg from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, More preferably, it is the range of 1000-3500 mmol/kg, More preferably, it is the range of 1100-3000 mmol/kg, and the range of 1150-2500 mmol/kg. It should be noted that the content of the urethane bond of the above-mentioned urethane resin (A) represents the following polyisocyanate (a1), polyol (a2), and the urethane bond used in the production of the urethane having a hydrophilic group. The value calculated from the raw material of the resin and the added amount of the chain extender (a3).
作为上述氨基甲酸酯树脂(A)的脲键的含量，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选为315～850mmol/kg的范围，更优选为350～830mmol/kg的范围，进一步优选为400～800mmol/kg的范围，进一步优选为410～770mmol/kg的范围。应予说明，上述氨基甲酸酯树脂(A)的脲键的含量表示根据上述多异氰酸酯(a1)、多元醇(a2)、用于制造具有亲水性基团的氨基甲酸酯树脂的原料和扩链剂(a3)的加入量而算出的值。The urea bond content of the urethane resin (A) is preferably in the range of 315 to 850 mmol/kg, more preferably The range of 350-830 mmol/kg, More preferably, it is the range of 400-800 mmol/kg, More preferably, it is the range of 410-770 mmol/kg. In addition, the content of the urea bond of the said urethane resin (A) represents the raw material used for manufacturing the urethane resin which has a hydrophilic group based on the said polyisocyanate (a1), polyol (a2), The value calculated from the added amount of the chain extender (a3).
作为上述氨基甲酸酯树脂(A)的脂环结构的含量，从得到更优异的耐化学试剂性、耐磨损性和耐候性的观点出发，优选为500～3000mmol/kg的范围，更优选为600～2900mmol/kg的范围，进一步优选为700～2700mmol/kg的范围。应予说明，上述氨基甲酸酯树脂(A)的脂环结构的含量表示根据上述多异氰酸酯(a1)、多元醇(a2)、用于制造具有亲水性基团的氨基甲酸酯树脂的原料和扩链剂(a3)的加入量而算出的值。The content of the alicyclic structure of the above-mentioned urethane resin (A) is preferably in the range of 500 to 3000 mmol/kg, and more preferably It is the range of 600-2900 mmol/kg, More preferably, it is the range of 700-2700 mmol/kg. It should be noted that the content of the alicyclic structure of the above-mentioned urethane resin (A) represents the content of the above-mentioned polyisocyanate (a1), polyol (a2), and the amount used for producing a urethane resin having a hydrophilic group. Value calculated from the added amount of raw materials and chain extender (a3).
作为上述氨基甲酸酯树脂(A)的含量，从涂覆性、操作性和保存稳定性的观点出发，优选为氨基甲酸酯树脂组合物中3～50质量％的范围，更优选为5～30质量％的范围。The content of the urethane resin (A) is preferably in the range of 3 to 50% by mass in the urethane resin composition, more preferably 5% by mass, from the viewpoint of coatability, handleability, and storage stability. ~30% by mass.
作为上述水(B)，可以使用离子交换水、蒸馏水等。作为上述水(B)的含量，从氨基甲酸酯树脂组合物的涂覆性、操作性和保存稳定性的观点出发，优选为氨基甲酸酯树脂组合物中30～95质量％的范围，更优选为50～90质量％的范围。As said water (B), ion-exchange water, distilled water, etc. can be used. The content of the above-mentioned water (B) is preferably in the range of 30 to 95% by mass in the urethane resin composition from the viewpoint of coatability, handleability, and storage stability of the urethane resin composition. More preferably, it is the range of 50-90 mass %.
作为上述硅酮化合物(C)，在得到优异的耐磨损性方面，必须使用数均分子量为15万以上且小于33万的硅酮化合物。通过如此地使用较高分子量的硅酮化合物，从而能够形成表面强度高、摩擦系数小的涂膜，得到优异的耐磨损性。作为上述硅酮化合物(C)的数均分子量，从得到更优异的耐磨损性的观点出发，优选为20万～30万的范围，更优选为22万～27万的范围。应予说明，上述硅酮化合物(C)的数均分子量表示通过凝胶渗透色谱(GPC)法所测得的值，具体而言，在实施例中示出其测定方法。As the silicone compound (C), it is necessary to use a silicone compound having a number average molecular weight of 150,000 or more and less than 330,000 in order to obtain excellent wear resistance. By using such a relatively high molecular weight silicone compound, a coating film with high surface strength and a small friction coefficient can be formed, and excellent abrasion resistance can be obtained. The number average molecular weight of the silicone compound (C) is preferably in the range of 200,000 to 300,000, and more preferably in the range of 220,000 to 270,000, from the viewpoint of obtaining more excellent wear resistance. In addition, the number average molecular weight of the said silicone compound (C) shows the value measured by the gel permeation chromatography (GPC) method, Specifically, the measuring method is shown in the Example.
作为上述硅酮化合物(C)，具体而言，例如可以使用：聚二甲基硅氧烷、聚甲基苯基硅氧烷、聚甲基氢硅氧烷、聚甲基苯基氢硅氧烷；它们的改性物；这些硅酮化合物与丙烯酸的共聚物等。这些硅酮化合物可以单独使用，也可以并用2种以上。其中，从得到更优异的耐磨损性的观点出发，优选使用聚二甲基硅氧烷。As the above-mentioned silicone compound (C), specifically, for example, polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, polymethylphenylhydrogensiloxane, polymethylphenylhydrogensiloxane, alkanes; their modified products; copolymers of these silicone compounds and acrylic acid, etc. These silicone compounds may be used alone or in combination of two or more. Among them, polydimethylsiloxane is preferably used from the viewpoint of obtaining more excellent abrasion resistance.
从与水(B)的亲和性的观点出发，上述硅酮化合物(C)优选采用分散于水(B)的乳液的形态。另外，此时，可以含有公知的表面活性剂。From the viewpoint of affinity with water (B), the silicone compound (C) is preferably in the form of an emulsion dispersed in water (B). In addition, at this time, a known surfactant may be contained.
作为上述硅酮化合物(C)的含量(＝硅酮化合物(C)固体成分)，从得到更优异的耐磨损性的观点出发，优选为0.01～10质量％的范围，更优选为0.1～7质量％的范围，进一步优选为0.5～5质量％的范围。The content of the silicone compound (C) (=solid content of the silicone compound (C)) is preferably in the range of 0.01 to 10% by mass, more preferably 0.1 to 10% by mass, from the viewpoint of obtaining more excellent wear resistance. The range of 7 mass %, More preferably, it is the range of 0.5-5 mass %.
本发明的氨基甲酸酯树脂组合物含有上述氨基甲酸酯树脂(A)、水(B)和硅酮化合物(C)作为必须成分，但也可以根据需要使用其他的添加剂。The urethane resin composition of the present invention contains the above-mentioned urethane resin (A), water (B) and silicone compound (C) as essential components, but other additives may be used as necessary.
作为上述其他的添加剂，例如可以使用：填料(D)、交联剂(E)、乳化剂、消泡剂、流平剂、增稠剂、粘弹性调节剂、消泡剂、湿润剂、分散剂、防腐剂、增塑剂、渗透剂、香料、杀菌剂、杀螨剂、防霉剂、紫外线吸收剂、抗氧化剂、防静电剂、阻燃剂、染料、颜料(例如钛白、铁丹、酞菁、炭黑、永固黄等)等。这些添加剂可以单独使用，也可以并用2种以上。As the above-mentioned other additives, for example, fillers (D), crosslinking agents (E), emulsifiers, defoamers, leveling agents, thickeners, viscoelastic modifiers, defoamers, wetting agents, dispersants Agents, preservatives, plasticizers, penetrating agents, fragrances, bactericides, acaricides, anti-fungal agents, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (such as titanium dioxide, iron red , phthalocyanine, carbon black, permanent yellow, etc.), etc. These additives may be used alone or in combination of two or more.
作为上述其他的添加剂，在使用本发明的氨基甲酸酯树脂组合物作为表面处理剂的情况下，为了对其涂膜赋予哑光感，优选含有填料(D)，为了提高涂膜的机械强度，优选含有交联剂(E)。As the above-mentioned other additives, when the urethane resin composition of the present invention is used as a surface treatment agent, in order to impart a matte feeling to the coating film, it is preferable to contain a filler (D), in order to improve the mechanical strength of the coating film , preferably contain a crosslinking agent (E).
作为上述填料(D)，例如可以使用二氧化硅粒子、有机微珠、碳酸钙、碳酸镁、碳酸钡、滑石、氢氧化铝、硫酸钙、高岭土、云母(日文：雲母)、石棉、云母(日文：マイカ)、硅酸钙、硅酸铝等。这些填料可以单独使用，也可以并用2种以上。As the filler (D), for example, silica particles, organic microbeads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica (Japanese: mica), asbestos, mica ( Japanese: マイカ), calcium silicate, aluminum silicate, etc. These fillers may be used alone or in combination of two or more.
作为上述二氧化硅粒子，例如可以使用干式二氧化硅、湿式二氧化硅等。其中，从散射效果高、光泽值的调整范围宽的方面考虑，优选干式二氧化硅。作为这些二氧化硅粒子的平均粒径，优选为2～14μm的范围，更优选为3～12μm的范围。应予说明，上述二氧化硅粒子的平均粒径表示在粒度分布测定结果的累积粒子量曲线中，其累积量占50％时的粒径(粒度分布中的以D50计的粒径)。As said silica particle, dry type silica, wet type silica etc. can be used, for example. Among them, dry silica is preferable in terms of high scattering effect and wide adjustment range of gloss value. The average particle diameter of these silica particles is preferably in the range of 2 to 14 μm, and more preferably in the range of 3 to 12 μm. In addition, the average particle diameter of the above-mentioned silica particles represents the particle diameter (particle diameter in terms of D50 in the particle size distribution) when the cumulative amount accounts for 50% in the cumulative particle amount curve of the particle size distribution measurement result.
作为上述有机微珠，例如可以使用丙烯酸系微珠、氨基甲酸酯微珠、硅微珠、烯烃微珠等。As the organic microbeads, for example, acrylic microbeads, urethane microbeads, silicon microbeads, olefin microbeads and the like can be used.
上述填料(D)的使用量可以根据要赋予的哑光感适当确定，例如，相对于氨基甲酸酯树脂(A)100质量份，优选为1～30质量份的范围，更优选为3～10质量份的范围。The amount of the filler (D) used can be appropriately determined according to the matte feeling to be imparted. For example, it is preferably in the range of 1 to 30 parts by mass, more preferably 3 to 30 parts by mass, based on 100 parts by mass of the urethane resin (A). 10 parts by mass.
作为上述交联剂(E)，例如可以使用：异氰酸酯交联剂、环氧交联剂、碳二亚胺交联剂、噁唑烷交联剂、噁唑啉交联剂、三聚氰胺交联剂等。这些交联剂可以单独使用，也可以并用2种以上。As the crosslinking agent (E), for example, isocyanate crosslinking agents, epoxy crosslinking agents, carbodiimide crosslinking agents, oxazolidine crosslinking agents, oxazoline crosslinking agents, and melamine crosslinking agents can be used. wait. These crosslinking agents may be used alone or in combination of two or more.
作为上述交联剂(E)的使用量，例如，相对于上述氨基甲酸酯树脂(A)100质量份，优选为5～40质量份的范围，更优选为10～30质量份的范围。As the usage-amount of the said crosslinking agent (E), it is preferable that it is the range of 5-40 mass parts with respect to 100 mass parts of said urethane resins (A), and it is more preferable that it is the range of 10-30 mass parts, for example.
以上，本发明的氨基甲酸酯树脂组合物能够得到耐化学试剂性优异的覆膜。因此，本发明的氨基甲酸酯树脂组合物能够适合用作合成皮革、聚氯乙烯(PVC)皮革、热塑性烯烃树脂(TPO)皮革、仪表盘、仪表板等各种物品的表面处理剂。As mentioned above, the urethane resin composition of this invention can obtain the coating film excellent in chemical resistance. Therefore, the urethane resin composition of the present invention can be suitably used as a surface treatment agent for various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboards, and instrument panels.
本发明的物品具有利用上述表面处理剂形成的层。The article of the present invention has a layer formed using the above-mentioned surface treatment agent.
作为上述物品的具体例，例如可举出：使用了合成皮革、人工皮革、天然皮革、聚氯乙烯(PVC)皮革的汽车内部装饰片材、运动鞋、服装、家具、热塑性烯烃(TPO)皮革、仪表盘、仪表板等。Specific examples of the above articles include, for example, synthetic leather, artificial leather, natural leather, and polyvinyl chloride (PVC) leather, automotive interior trim sheets, sports shoes, clothing, furniture, and thermoplastic olefin (TPO) leather. , Dashboard, Dashboard, etc.
作为利用上述表面处理剂形成的层的厚度，例如为0.1～100μm的范围。The thickness of the layer formed by the surface treatment agent is, for example, in the range of 0.1 to 100 μm.
实施例Example
以下，使用实施例，更详细地说明本发明。Hereinafter, the present invention will be described in more detail using examples.
[合成例1]氨基甲酸酯树脂(A-1)水分散体的制备[Synthesis Example 1] Preparation of Urethane Resin (A-1) Aqueous Dispersion
在具备搅拌机、温度计和氮回流管的四口烧瓶中加入甲乙酮250质量份和辛酸亚锡0.001质量份，接下来，加入聚碳酸酯多元醇-1(以1，4-丁二醇和1，6-己二醇为原料，数均分子量：1000)200质量份、2，2-二羟甲基丙酸15质量份、异佛尔酮二异氰酸酯49质量份、六亚甲基二异氰酸酯34质量份，在70℃反应1小时，得到氨基甲酸酯预聚物的甲乙酮溶液。Add 250 parts by mass of methyl ethyl ketone and 0.001 part by mass of stannous octoate in a four-necked flask equipped with a stirrer, a thermometer and a nitrogen reflux tube, and then add polycarbonate polyol-1 (with 1,4-butanediol and 1,6 - Hexylene glycol as raw material, number average molecular weight: 1000) 200 parts by mass, 15 parts by mass of 2,2-dimethylol propionic acid, 49 parts by mass of isophorone diisocyanate, 34 parts by mass of hexamethylene diisocyanate , reacted at 70° C. for 1 hour to obtain a methyl ethyl ketone solution of the urethane prepolymer.
接下来，在该氨基甲酸酯预聚物的甲乙酮溶液中混合肼6.8质量份、三乙胺15质量份后，加入离子交换水820质量份，得到氨基甲酸酯树脂(A-1)分散于水中的乳化液。Next, after mixing 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine in the methyl ethyl ketone solution of the urethane prepolymer, 820 parts by mass of ion-exchanged water was added to obtain a urethane resin (A-1) dispersion emulsion in water.
接下来，从上述乳化液中蒸馏除去甲乙酮，进一步加入离子交换水，由此得到不挥发成分为30质量％的氨基甲酸酯树脂(A-1)水分散体。Next, methyl ethyl ketone was distilled off from the said emulsion liquid, and ion-exchange water was further added, and the urethane resin (A-1) aqueous dispersion whose nonvolatile matter was 30 mass % was obtained.
得到的氨基甲酸酯树脂(A-1)的氨基甲酸酯键的含量为2052mmol/kg，脲键的含量为698mmol/kg，脂环结构的含量为715mmol/kg。The obtained urethane resin (A-1) had a urethane bond content of 2052 mmol/kg, a urea bond content of 698 mmol/kg, and an alicyclic structure content of 715 mmol/kg.
[合成例2]氨基甲酸酯树脂(A-2)水分散体的制备[Synthesis Example 2] Preparation of Urethane Resin (A-2) Aqueous Dispersion
在具备搅拌机、温度计和氮回流管的四口烧瓶中加入甲乙酮250质量份和辛酸亚锡0.001质量份，接下来，加入聚碳酸酯多元醇-3(以1，6-己二醇为原料，数均分子量：2000)220质量份、2，2-二羟甲基丙酸12质量份、二环己基甲烷二异氰酸酯70质量份，在70℃反应1小时，得到氨基甲酸酯预聚物的甲乙酮溶液。Add 250 mass parts of methyl ethyl ketone and 0.001 mass part of stannous octoate in the four-necked flask that possesses stirrer, thermometer and nitrogen reflux pipe, next, add polycarbonate polyol-3 (with 1,6-hexanediol as raw material, Number average molecular weight: 2000) 220 parts by mass, 12 parts by mass of 2,2-dimethylolpropionic acid, 70 parts by mass of dicyclohexylmethane diisocyanate, react at 70° C. for 1 hour to obtain a urethane prepolymer Methyl ethyl ketone solution.
接下来，在该氨基甲酸酯预聚物的甲乙酮溶液中混合哌嗪4.5质量份、三乙胺9质量份后，加入离子交换水880质量份，得到氨基甲酸酯树脂(A-2)分散于水中的乳化液。Next, after mixing 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine in the methyl ethyl ketone solution of the urethane prepolymer, 880 parts by mass of ion-exchanged water was added to obtain a urethane resin (A-2) Emulsion dispersed in water.
接下来，从上述乳化液中蒸馏除去甲乙酮，进一步加入离子交换水，由此得到不挥发成分为32质量％的氨基甲酸酯树脂(A-2)水分散体。Next, methyl ethyl ketone was distilled off from the said emulsion liquid, and ion-exchange water was further added, and the urethane resin (A-2) aqueous dispersion whose nonvolatile matter was 32 mass % was obtained.
得到的氨基甲酸酯树脂(A-2)的氨基甲酸酯键的含量为1278mmol/kg，脲键的含量为435mmol/kg，脂环结构的含量为1713mmol/kg。The obtained urethane resin (A-2) had a urethane bond content of 1278 mmol/kg, a urea bond content of 435 mmol/kg, and an alicyclic structure content of 1713 mmol/kg.
[合成例3]氨基甲酸酯树脂(A-3)水分散体的制备[Synthesis Example 3] Preparation of Urethane Resin (A-3) Aqueous Dispersion
在具备搅拌机、温度计和氮回流管的四口烧瓶中加入甲乙酮250质量份和辛酸亚锡0.001质量份，接下来，加入聚碳酸酯多元醇-4(以1，6-己二醇为原料，数均分子量：2000)138质量份、聚碳酸酯多元醇-5(以1，6-己二醇为原料，数均分子量：500)55质量份、2，2-二羟甲基丙酸13质量份、二环己基甲烷二异氰酸酯100质量份，在70℃反应1小时，得到氨基甲酸酯预聚物的甲乙酮溶液。Add 250 mass parts of methyl ethyl ketone and 0.001 mass part of stannous octoate in the four-necked flask that possesses stirrer, thermometer and nitrogen reflux tube, next, add polycarbonate polyol-4 (with 1,6-hexanediol as raw material, Number average molecular weight: 2000) 138 parts by mass, polycarbonate polyol-5 (using 1,6-hexanediol as raw material, number average molecular weight: 500) 55 parts by mass, 2,2-dimethylolpropionic acid 13 Parts by mass and 100 parts by mass of dicyclohexylmethane diisocyanate were reacted at 70° C. for 1 hour to obtain a methyl ethyl ketone solution of a urethane prepolymer.
接下来，在该氨基甲酸酯预聚物的甲乙酮溶液中混合哌嗪5.6质量份、三乙胺10质量份后，加入离子交换水880质量份，得到氨基甲酸酯树脂(A-3)分散于水中的乳化液。Next, after mixing 5.6 parts by mass of piperazine and 10 parts by mass of triethylamine in the methyl ethyl ketone solution of the urethane prepolymer, 880 parts by mass of ion-exchanged water was added to obtain a urethane resin (A-3) Emulsion dispersed in water.
接下来，从上述乳化液中蒸馏除去甲乙酮，进一步加入离子交换水，由此得到不挥发成分为30质量％的氨基甲酸酯树脂(A-3)水分散体。Next, methyl ethyl ketone was distilled off from the said emulsion liquid, and ion-exchange water was further added, and the urethane resin (A-3) aqueous dispersion whose nonvolatile matter was 30 mass % was obtained.
得到的氨基甲酸酯树脂(A-3)的氨基甲酸酯键的含量为1747mmol/kg，脲键的含量为576mmol/kg，脂环结构的含量为2341mmol/kg。The obtained urethane resin (A-3) had a urethane bond content of 1747 mmol/kg, a urea bond content of 576 mmol/kg, and an alicyclic structure content of 2341 mmol/kg.
[实施例1][Example 1]
将合成例1中得到的氨基甲酸酯树脂(A-1)水分散体35质量份、碳二亚胺交联剂(日清纺化学株式会社制“CARBODILITEV-02-L2”)3质量份、填料(EVONIK DEGUSSA公司制“ACEMATTTS 100”，通过干式法制造的二氧化硅粒子，平均粒径：10μm)2质量份、聚二甲基硅氧烷的水分散体(聚二甲基硅氧烷的含有率；65质量％，数均分子量；25.5万)3质量份、水57质量份混合，由此得到氨基甲酸酯树脂组合物。35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, and 3 parts by mass of a carbodiimide crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITEV-02-L2") , filler ("ACEMATTTS 100" manufactured by EVONIK DEGUSSA company, silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane Content rate of oxane; 65% by mass, number average molecular weight; 255,000) 3 parts by mass, and 57 parts by mass of water were mixed to obtain a urethane resin composition.
[实施例2][Example 2]
将合成例1中得到的氨基甲酸酯树脂(A-1)水分散体35质量份、碳二亚胺交联剂(日清纺化学株式会社制“CARBODILITEV-02-L2”)3质量份、填料(EVONIK DEGUSSA公司制“ACEMATTTS 100”，通过干式法制造的二氧化硅粒子，平均粒径：10μm)2质量份、聚二甲基硅氧烷的水分散体(聚二甲基硅氧烷的含有率；65质量％，数均分子量；25.5万)6质量份、水54质量份混合，由此得到氨基甲酸酯树脂组合物。35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, and 3 parts by mass of a carbodiimide crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITEV-02-L2") , filler ("ACEMATTTS 100" manufactured by EVONIK DEGUSSA company, silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane A urethane resin composition was obtained by mixing 6 parts by mass of oxane content; 65% by mass, number average molecular weight; 255,000) and 54 parts by mass of water.
[实施例3][Example 3]
将合成例1中得到的氨基甲酸酯树脂(A-1)水分散体35质量份、碳二亚胺交联剂(日清纺化学株式会社制“CARBODILITEV-02-L2”)3质量份、填料(EVONIK DEGUSSA公司制“ACEMATTTS 100”，通过干式法制造的二氧化硅粒子，平均粒径：10μm)2质量份、聚二甲基硅氧烷的水分散体(聚二甲基硅氧烷的含有率；65质量％，数均分子量；25.5万)0.5质量份、水59.5质量份混合，由此得到氨基甲酸酯树脂组合物。35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, and 3 parts by mass of a carbodiimide crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITEV-02-L2") , filler ("ACEMATTTS 100" manufactured by EVONIK DEGUSSA company, silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane Oxane content: 65% by mass, number average molecular weight: 255,000) 0.5 parts by mass, and 59.5 parts by mass of water were mixed to obtain a urethane resin composition.
[实施例4][Example 4]
将合成例1中得到的氨基甲酸酯树脂(A-2)水分散体35质量份、碳二亚胺交联剂(日清纺化学株式会社制“CARBODILITEV-02-L2”)3质量份、填料(EVONIK DEGUSSA公司制“ACEMATTTS 100”，通过干式法制造的二氧化硅粒子，平均粒径：10μm)2质量份、聚二甲基硅氧烷的水分散体(聚二甲基硅氧烷的含有率；65质量％，数均分子量；20万)3质量份、水57质量份混合，由此得到氨基甲酸酯树脂组合物。35 parts by mass of the aqueous dispersion of the urethane resin (A-2) obtained in Synthesis Example 1, and 3 parts by mass of a carbodiimide crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITEV-02-L2") , filler ("ACEMATTTS 100" manufactured by EVONIK DEGUSSA company, silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane Content rate of oxane; 65% by mass, number average molecular weight; 200,000) 3 parts by mass and 57 parts by mass of water were mixed to obtain a urethane resin composition.
[实施例5][Example 5]
将合成例1中得到的氨基甲酸酯树脂(A-3)水分散体35质量份、碳二亚胺交联剂(日清纺化学株式会社制“CARBODILITEV-02-L2”)3质量份、填料(EVONIK DEGUSSA公司制“ACEMATTTS 100”，通过干式法制造的二氧化硅粒子，平均粒径：10μm)2质量份、聚二甲基硅氧烷的水分散体(聚二甲基硅氧烷的含有率；65质量％，数均分子量；30万)3质量份、水57质量份混合，由此得到氨基甲酸酯树脂组合物。35 parts by mass of the aqueous dispersion of the urethane resin (A-3) obtained in Synthesis Example 1, and 3 parts by mass of a carbodiimide crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITEV-02-L2") , filler ("ACEMATTTS 100" manufactured by EVONIK DEGUSSA company, silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane Content rate of oxane; 65% by mass, number average molecular weight; 300,000) 3 parts by mass and 57 parts by mass of water were mixed to obtain a urethane resin composition.
[比较例1][Comparative example 1]
除了在实施例1中不包含聚二甲基硅氧烷的水分散体以外，与实施例1同样地操作，得到氨基甲酸酯树脂组合物。Except not including the aqueous dispersion of polydimethylsiloxane in Example 1, it carried out similarly to Example 1, and obtained the urethane resin composition.
[比较例2][Comparative example 2]
将合成例1中得到的氨基甲酸酯树脂(A-1)水分散体35质量份、碳二亚胺交联剂(日清纺化学株式会社制“CARBODILITEV-02-L2”)3质量份、填料(EVONIK DEGUSSA公司制“ACEMATTTS 100”，通过干式法制造的二氧化硅粒子，平均粒径：10μm)2质量份、聚二甲基硅氧烷的水分散体(聚二甲基硅氧烷的含有率；65质量％，数均分子量；10万)3质量份、水57质量份混合，由此得到氨基甲酸酯树脂组合物。35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, and 3 parts by mass of a carbodiimide crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITEV-02-L2") , filler ("ACEMATTTS 100" manufactured by EVONIK DEGUSSA company, silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane Content rate of oxane; 65% by mass, number average molecular weight; 100,000) 3 parts by mass and 57 parts by mass of water were mixed to obtain a urethane resin composition.
[比较例3][Comparative example 3]
将合成例1中得到的氨基甲酸酯树脂(A-1)水分散体35质量份、碳二亚胺交联剂(日清纺化学株式会社制“CARBODILITEV-02-L2”)3质量份、填料(EVONIK DEGUSSA公司制“ACEMATTTS 100”，通过干式法制造的二氧化硅粒子，平均粒径：10μm)2质量份、水57质量份混合后，添加聚二甲基硅氧烷的水分散体(聚二甲基硅氧烷的含有率；65质量％，数均分子量；50万)3质量份，但未混合，无法进行耐磨损性的试验。35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, and 3 parts by mass of a carbodiimide crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITEV-02-L2") After mixing 2 parts by mass of a filler ("ACEMATTTS 100" manufactured by EVONIK DEGUSSA, silica particles produced by a dry method, average particle diameter: 10 μm), and 57 parts by mass of water, add polydimethylsiloxane to the water The dispersion (content rate of polydimethylsiloxane; 65% by mass, number average molecular weight; 500,000) was 3 parts by mass, but it was not mixed, and the wear resistance test could not be performed.
[数均分子量的测定方法(1)][Measuring method of number average molecular weight (1)]
合成例中使用的多元醇的数均分子量表示通过凝胶渗透色谱(GPC)法，在下述条件下测定而得到的值。The number average molecular weight of the polyhydric alcohol used in the synthesis example shows the value measured by the gel permeation chromatography (GPC) method under the following conditions.
测定装置：高速GPC装置(东曹株式会社制“HLC-8220GPC”)色谱柱：串联连接东曹株式会社制的下述色谱柱来使用。Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
“TSKgel G5000”(7.8mmI.D.×30cm)×1根"TSKgel G5000" (7.8mmI.D.×30cm)×1
“TSKgel G4000”(7.8mmI.D.×30cm)×1根"TSKgel G4000" (7.8mmI.D.×30cm)×1
“TSKgel G3000”(7.8mmI.D.×30cm)×1根"TSKgel G3000" (7.8mmI.D.×30cm)×1
“TSKgel G2000”(7.8mmI.D.×30cm)×1根"TSKgel G2000" (7.8mmI.D.×30cm)×1
检测器：RI(差示折射计)Detector: RI (differential refractometer)
柱温：40℃Column temperature: 40°C
洗脱液：四氢呋喃(THF)Eluent: Tetrahydrofuran (THF)
流速：1.0mL/分钟Flow rate: 1.0mL/min
注入量：100μL(试样浓度0.4质量％的四氢呋喃溶液)Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
标准试样：使用下述的标准聚苯乙烯制作校正曲线。Standard sample: A calibration curve was prepared using the following standard polystyrene.
(标准聚苯乙烯)(standard polystyrene)
东曹株式会社制“TSKgel标准聚苯乙烯A-500”"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯A-1000”"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯A-2500”"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯A-5000”"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-1”"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-2”"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-4”"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-10”"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-20”"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-40”"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-80”"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-128”"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-288”"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
东曹株式会社制“TSKgel标准聚苯乙烯F-550”"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
[数均分子量的测定方法(2)][Measuring method of number average molecular weight (2)]
硅酮化合物(C)的数均分子量表示通过GPC(凝胶渗透色谱)法，在下述条件下测定而得到的值。The number average molecular weight of a silicone compound (C) shows the value measured by the GPC (gel permeation chromatography) method under the following conditions.
测定装置：高速GPC装置(东曹株式会社制“HLC-8220GPC”)Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
色谱柱：串联连接东曹株式会社制的下述色谱柱来使用。Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
“TSKgel GMHXL”(7.8mmI.D.×30cm)×4根"TSKgel GMHXL" (7.8mmI.D.×30cm)×4
检测器：RI(差示折射计)Detector: RI (differential refractometer)
柱温：40℃Column temperature: 40°C
洗脱液：四氢呋喃(THF)Eluent: Tetrahydrofuran (THF)
流速：1.0mL/分钟Flow rate: 1.0mL/min
注入量：100μLInjection volume: 100μL
浓度：分析试样：4mg/mL的四氢呋喃溶液Concentration: Analytical sample: 4mg/mL tetrahydrofuran solution
标准物质：1mg/mL的四氢呋喃溶液Standard substance: 1mg/mL tetrahydrofuran solution
标准物质：使用下述的具环氧乙烷/聚乙二醇制作校正曲线。Standard substance: Use the following ethylene oxide/polyethylene glycol to make a calibration curve.
标准物质standard material
<聚环氧乙烷〉<Polyethylene oxide>
东曹株式会社制“TSKgel标准聚环氧乙烷SE-70”Tosoh Corporation "TSKgel Standard Polyethylene Oxide SE-70"
东曹株式会社制“TSKgel标准聚环氧乙烷SE-30”Tosoh Corporation "TSKgel standard polyethylene oxide SE-30"
东曹株式会社制“TSKgel标准聚环氧乙烷SE-15”Tosoh Corporation "TSKgel standard polyethylene oxide SE-15"
东曹株式会社制“TSKgel标准聚环氧乙烷SE-8”Tosoh Corporation "TSKgel standard polyethylene oxide SE-8"
东曹株式会社制“TSKgel标准聚环氧乙烷SE-5”Tosoh Corporation "TSKgel standard polyethylene oxide SE-5"
东曹株式会社制“TSKgel标准聚环氧乙烷SE-2”Tosoh Corporation "TSKgel standard polyethylene oxide SE-2"
<聚乙二醇><polyethylene glycol>
聚乙二醇6000polyethylene glycol 6000
聚乙二醇3000polyethylene glycol 3000
聚乙二醇1000polyethylene glycol 1000
聚乙二醇600Polyethylene glycol 600
[耐磨损性的评价方法][Evaluation method of wear resistance]
使用50μm棒涂机在脱模纸上涂覆实施例和比较例中得到的氨基甲酸酯树脂组合物，在120℃下用传动烘箱(日文：ギアオーブン)干燥2分钟，得到评价用样品。对于该评价样品，使用平面磨损试验机(INTEC株式会社制“AR-4S”)，使用2kg载荷、6号帆布进行评价。具体而言，在平面磨损试验机上依次放置4.5mmφ的不锈钢丝、缓冲材料(厚度；10mm，压缩应力；1N/cm2)、试验片，拉伸5％并进行固定。每1千次观察该样品的磨损状态，测定直至涂膜破裂素材露出为止的次数。应予说明，将无法进行耐磨损性的评价的情况记为“-”。The urethane resin compositions obtained in Examples and Comparative Examples were coated on release paper using a 50 μm bar coater, and dried in a transmission oven (Japanese: ギアリーブン) at 120° C. for 2 minutes to obtain samples for evaluation. The evaluation sample was evaluated using a flat abrasion tester ("AR-4S" manufactured by INTEC Corporation) with a load of 2 kg and a No. 6 canvas. Specifically, a 4.5 mmφ stainless steel wire, a buffer material (thickness; 10 mm, compressive stress: 1 N/cm 2 ), and a test piece were sequentially placed on a flat wear tester, stretched by 5%, and fixed. The wear state of the sample was observed every 1,000 times, and the number of times until the coating film cracked material was exposed was measured. In addition, the case where the evaluation of wear resistance was not possible was described as "-".
[表1][Table 1]
[表2][Table 2]
表1和2中的“PDMSi”表示聚二甲基硅氧烷。"PDMSi" in Tables 1 and 2 means polydimethylsiloxane.
可知本发明的氨基甲酸酯树脂组合物具有优异的耐磨损性。It can be seen that the urethane resin composition of the present invention has excellent abrasion resistance.
另一方面，比较例1是完全没有使用硅酮化合物(C)的方式，耐磨损性不充分。On the other hand, in Comparative Example 1, the silicone compound (C) was not used at all, and the abrasion resistance was insufficient.
比较例2是使用具有低于本发明中规定的范围的数均分子量的硅酮化合物来代替硅酮化合物(C)的方式，耐磨损性不充分。In Comparative Example 2, a silicone compound having a number average molecular weight lower than the range specified in the present invention was used instead of the silicone compound (C), and the abrasion resistance was insufficient.
比较例3是使用具有超过本发明中规定的范围的数均分子量的硅酮化合物来代替硅酮化合物(C)的方式，无法很好地混合为氨基甲酸酯树脂组合物，难以用作表面处理剂。Comparative Example 3 is a method in which a silicone compound having a number-average molecular weight exceeding the range specified in the present invention is used instead of the silicone compound (C), and it cannot be well mixed into a urethane resin composition, and it is difficult to use as a surface treatment agent.
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| JP3292065B2 (en) * | 1996-10-02 | 2002-06-17 | 信越化学工業株式会社 | Silicone-modified polyurethane elastomer and method for producing the same |
| CN100347252C (en) * | 2003-04-30 | 2007-11-07 | 国家淀粉及化学投资控股公司 | Waterbased high abrasion resistant coating |
| JP2005220321A (en) * | 2004-02-09 | 2005-08-18 | Dainichiseika Color & Chem Mfg Co Ltd | Fine silica particle-dispersed hydrophilic polyurethane resin composition and method for producing the same |
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| US8476330B2 (en) * | 2007-07-13 | 2013-07-02 | Momentive Performance Materials Inc. | Polyurethane foam containing synergistic surfactant combinations and process for making same |
| CN101469055A (en) * | 2007-12-26 | 2009-07-01 | 汉高股份两合公司 | Active organosilicon-polyurethane performed polymer and solvent-free active organosilicon-polyurethane emulsion prepared thereby |
| WO2009102035A1 (en) * | 2008-02-15 | 2009-08-20 | Asahi Kasei E-Materials Corporation | Resin composition |
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